Catalytic and Asymmetric Fluorolactonisations of Carboxylic Acids through Anion Phase Transfer

Catalytic fluorolactonisations of aromatic carboxylic acids have been developed. The reactions proceed under mild conditions using the commercially available reagent Selectfluor. A weak phase transfer of the reagent mediated by Na₂CO₃ allows the reaction to be conducted in non‐polar solvents. Furthermore, by the use of a catalytic amount of (DHQ)₂PHAL (hydroquinine 1,4‐phthalazinediyl diether), the first asymmetric fluorolactonisation has been achieved. The corresponding isobenzofuran core can be found in many biologically active molecules.     

Probing Relaxation Dynamics in Five-Coordinate Dysprosium Single-Molecule Magnets

A new family of five-coordinate lanthanide single-molecule magnets (Ln SMMs) [Dy(Mes*O)₂(THF)₂X] (Mes*=2,4,6-tri-tert-butylphenyl; X=Cl, 1 ; Br, 2 ; I, 3 ) is reported with energy barriers to magnetic reversal >1200 K. The five-coordinate Dy^III ions have distorted square pyramidal geometries, with halide anions on the apex, and two Mes*O ligands mutually trans- to each other, and the two THF molecules forming the second trans- pair. These geometrical features lead to a large magnetic anisotropy in these complexes along the trans-Mes*O direction. QTM and Raman relaxation times are enhanced by varying the apex halide from Cl to Br to I, or by dilution in a diamagnetic yttrium analogue.     

Local disruption of DNA-base stacking by bulky base surrogates

A novel biphenyl base surrogate disrupts 2-aminopurine base stacking while maintaining duplex integrity.     

Structural characterization of microwave-synthesized zinc-substituted cobalt ferrite nanoparticles

Microwave combustion technique modified by post treatment procedure is used to synthesize single-phase spinel ferrites of cobalt, zinc, and substituted magnetic nanoparticles of typical size 390 Å. The post treatment does not alter the crystal structure but increases the crystallinity. This is confirmed by powder x-ray diffraction and Fourier Transform Infrared (FTIR) studies. Citric acid is used as a fuel. The fresh synthesized sample shows an impurity phase in x-ray and in FTIR. This is due to the unreacted citrate molecule adsorbed on the particle surface. It is shown that by treating the sample with 0.1 M HCl, we can eliminate the impurity phase, and one can obtain a pure single phase. The magnetization at 8 kOe increases by nearly 8% after the removal of impurity. In order to remove surface adsorbed OH^? ion, samples are treated with NaCl and heated to 200°C for four hours. The XRD result indicates that after the treatment neither the crystallite size nor the distribution changes, but it removes OH^? ion. This is also confirmed by FTIR analysis. Thus, this modified technique can be used to synthesize pure nanocrystalline samples of spinel ferrites.     

Viscosities of oxalic acid and its salts in water and binary aqueous mixtures of tetrahydrofuran at different temperatures

Relative viscosities for the solutions of oxalic acid and its salts, viz. ammonium oxalate, sodium oxalate and potassium oxalate, at different concentrations have been determined in water and in binary aqueous mixtures of tetrahydrofuran (THF) [5, 10, 15 and 20% by weight of THF] at 298.15 K, and in water and in 5% (w/w) THF + water at five different temperatures. The data have been evaluated using the Jones-Dole equation and the obtained parameters have been interpreted in terms of solute-solute and solute-solvent interactions. The activation parameters of viscous flow have been obtained which depicts the mechanism of viscous flow. The oxalic acid and its salts behave as structure breakers in water and in binary aqueous mixtures of THF.     

Cu(I)‐Catalyzed Efficient Synthesis of 2′‐Triazolo‐nucleoside Conjugates

A small library of thirty‐two 2′‐triazolyl uridine and 2′‐triazolyl‐5‐methyluridine has been synthesized by Cu(I)‐catalyzed condensation of 2′‐azido‐2′‐deoxyuridine and 2′‐azido‐2′‐deoxy‐5‐methyluridine with different alkynes and aryl propargyl ethers in almost quantitative yields. Triazolo‐nucleoside conjugates, which can be evaluated for different biological activity for suitable drug development, were unambiguously identified on the basis of ¹H NMR, ¹³C NMR, IR, and HRMS data analysis. These compounds have been synthesized for the first time and have not been reported in the literature earlier.